Studies of the Organic Reactions of Metal Carbonyls. VI. The Isomerization of Acylcobalt Carbonyls—The Effects of Solvents and of the Structure of the Acyl Group

Abstract

Abstract The reactions of n-butyryl chloride, isobutyryl bromide, α-ethylbutyryl chloride and n-caproyl chloride with potassium cobalt carbonylate have been studied. The results of this investigation are as follows. (1) It has been observed that solvents have great effects on the isomerization of butyrylcobalt carbonyls, as do the reaction temperature and the atmosphere. The rate and the equilibrium of this isomerization are remarkably affected by the solvents; in polar solvents, the equilibrium proportion of products (iso/normal) is almost zero in dioxane, 1/3 in ethyl acetate, and 1 in diethyl ether. This isomerization proceeds more rapidly under nitrogen atmosphere than under carbon monoxide. On the other hand, in nonpolar solvents such as benzene this isomerization apparently does not occur. (2) α-Ethylbutyrylcobalt carbonyl relatively readily isomerizes to n-caproylcobalt carbonyl. This isomerization is also accelerated under nitrogen atmosphere.